Hydrogen Peroxide → HCID 135899508, compound

HRID 1669002Notes

Reaction equation

HRID 1669002 reaction equation
OO.[CH2:3]([N:5]([CH2:23][CH3:24])[CH2:6][CH2:7][NH:8][C:9]1[N:10]=[N+:11]([O-:22])[C:12]2[C:21]3[CH2:20][CH2:19][CH2:18][C:17]=3[CH:16]=[CH:15][C:13]=2[N:14]=1)[CH3:4].C(O)(C(F)(F)F)=[O:26]>C(Cl)Cl.N>[CH2:23]([N:5]([CH2:3][CH3:4])[CH2:6][CH2:7][NH:8][C:9]1[N:10]=[N+:11]([O-:22])[C:12]2[C:21]3[CH2:20][CH2:19][CH2:18][C:17]=3[CH:16]=[CH:15][C:13]=2[N+:14]=1[O-:26])[CH3:24]

Participants

6

Reactant 3

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 25140478HCID 25140478, compound

Product 1

HCID 135899508HCID 135899508, compoundYield 41%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

H2O2 (70%, 0.37 mL, ca. 7.3 mmol) was added dropwise to a stirred solution of TFM (1.0 mL, 7.3 mmol) in DCM (10 mL) at 0° C. The solution was stirred at 0° C. for 5 min, warmed to 20° C. for 10 min, then cooled to 0° C. and added to a stirred solution of 1-oxide 8 (219 mg, 0.7 mmol) and TFA (280 μL, 3.6 mmol) in DCM (15 mL) at 0° C. The solution was stirred at 20° C. for 16 h, diluted with dilute aqueous NH3 solution (10 mL) and extracted with CHCl3 (4×50 mL). The combined organic fraction was dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (0-10%) of MeOH/DCM, to give 1,4-dioxide 9 (91 mg, 31%) as a red solid: mp (MeOH) 138-141° C.; 1H NMR δ 8.11 (d, J=8.7 Hz, 1H, H-5), 7.70 (d, J=8.7 Hz, 1H, H-6), 7.44 (br s, 1H, NH), 3.70 (br t, J=7.4 Hz, 2H, H-9), 3.58-3.63 (m, 2H, CH2N), 3.03 (br t, J=7.7 Hz, 2H, H-7), 2.77 (br dd, J=6.0, 5.8 Hz, 2H, CH2N), 2.63 (q, J=7.1 Hz, 4H, 2×CH2N), 2.22 (br p, J=7.7 Hz, 2H, H-8), 1.08 (t, J=7.1 Hz, 6H, 2×CH3); 13C NMR δ 149.0, 144.7, 138.6, 138.3, 132.7, 129.0, 115.7, 51.2, 46.8 (2), 38.8, 35.1, 32.9, 25.6, 11.7 (2). Anal. calcd for C16H23N5O2.½H2O: C, 58.9; H, 7.4; N, 21.5. Found: C, 59.2; H, 7.2; N, 21.5%.

Workup

  1. temperaturewarmed to 20° C. for 10 min
  2. temperaturecooled to 0° C.
  3. stirringThe solution was stirred at 20° C. for 16 h
  4. extractionextracted with CHCl3 (4×50 mL)
  5. customThe combined organic fraction was dried
  6. customthe solvent evaporated
  7. customThe residue was purified by chromatography
  8. washeluting with a gradient (0-10%) of MeOH/DCM

Sources & evidence

ORD record
ord-635a862c5b2b47c893a9313cdbb72c48
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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